• Title/Summary/Keyword: Mn substitution

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Kinetics and Mechanism of Substitution Reaction of $PPN^+(\eta^n-MeCp)Mn(CO)_2\;Cl^-$ with $PR_3$(R=Me, Et, OEt, $C_6H_5$)

  • Park, Yong Gwang;Lee, Yong Gu;Kim, Gyu Sik
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.138-142
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    • 1996
  • The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.

Nickel Substitution Effects on Nano-sized Co, Mn and MnZn Ferrites Synthesized by Sol-gel Method

  • Choi, Won-Ok;Kwon, Woo Hyun;Chae, Kwang Pyo;Lee, Young Bae
    • Journal of Magnetics
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    • v.21 no.1
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    • pp.40-45
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    • 2016
  • Nickel substituted nano-sized ferrite powders, $Co_{1-x}Ni_xFe_2O_4$, $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$), were fabricated using a sol-gel method, and their crystallographic and magnetic properties were subsequently compared. The lattice constants decreased as quantity of nickel substitution increased, while the particle size decreased in $Co_{1-x}Ni_xFe_2O_4$ ferrite but increased for the $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites. For the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$) ferrite powders, the $M{\ddot{o}}ssbauer$ spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. However, the $M{\ddot{o}}ssbauer$ spectrum of $Mn_{0.8}Zn_{0.1}Ni_{0.1}Fe_2O_4$ consisted of two Zeeman sextets and one single quadrupole doublet due to the ferrimagnetic and paramagnetic behavior. The area ratio of the $M{\ddot{o}}ssbauer$ spectra could be used to determine the cation distribution equation, and we also explain the variation in the $M{\ddot{o}}ssbauer$ parameters by using this cation distribution equation, the superexchange interaction and the particle size. The saturation magnetization decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. The coercivity decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. These variations could thus be explained by using the site distribution equations, particle sizes and spin magnetic moments of the substituted ions.

Electrochemical Performances of the Fluorine-Substituted on the 0.3Li2MnO3·0.7LiMn0.60Ni0.25Co0.15O2 Cathode Material

  • Kim, Seon-Min;Jin, Bong-Soo;Park, Gum-Jae;Kim, Hyun-Soo
    • Journal of Electrochemical Science and Technology
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    • v.5 no.3
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    • pp.87-93
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    • 2014
  • The fluorine-substituted $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode materials were synthesized by using the transition metal precursor, $LiOH{\cdot}H_2O$ and LiF. This was to facilitate the movement of lithium ions by forming more compact SEI layer and to reduce the dissolution of transition metals. The $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode material was sphere-shaped and each secondary particle had $10{\sim}15{\mu}m$ in size. The fluorine-substituted cathodes initially delivered low discharge capacity, but it gradually increased until 50th charge-discharge cycles. These results indicated that fluorine substitution gave positive effects on the structural stabilization and resistance reduction in materials.

The Synthesis of Na0.6Li0.6[Mn0.72Ni0.18Co0.10]O2 and its Electrochemical Performance as Cathode Materials for Li ion Batteries

  • Choi, Mansoo;Jo, In-Ho;Lee, Sang-Hun;Jung, Yang-Il;Moon, Jei-Kwon;Choi, Wang-Kyu
    • Journal of Electrochemical Science and Technology
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    • v.7 no.4
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    • pp.245-250
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    • 2016
  • The layered $Na_{0.6}Li_{0.6}[Mn_{0.72}Ni_{0.18}Co_{0.10}]O_2$ composite with well crystalized and high specific capacity is prepared by molten-salt method and using the substitution of Na for Li-ion battery. The effects of annealing temperature, time, Na contents, and electrochemical performance are investigated. In XRD analysis, the substitution of Na-ion resulted in the P2-$Na_{2/3}MO_2$ structure ($Na_{0.70}MO_{2.05}$), which co-exists in the $Na_{0.6}Li_{0.6}[Mn_{0.72}Ni_{0.18}Co_{0.10}]O_2$ composites. The discharge capacities of cathode materials exhibited $284mAhg^{-1}$ with higher initial coulombic efficiency.

Occurrence and Chemical Composition of Carbonate Mineral from Wallrock Alteration Zone of Janggun Pb-Zn Deposit (장군 연-아연 광상의 모암변질대내 탄산염 광물의 산상 및 화학조성)

  • Bong Chul Yoo
    • Korean Journal of Mineralogy and Petrology
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    • v.36 no.3
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    • pp.167-183
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    • 2023
  • The Janggun Pb-Zn deposit consists of Mn orebody, Pb-Zn orebody and Fe orebody. The Mn orebody composed of manganese carbonate orebody and manganese oxide orebody on the basis of their mineralogy and genesis. The geology of this deposit consists of Precambrian Weonnam formation, Yulri group, Paleozoic Jangsan formation, Dueumri formation, Janggum limestone formation, Dongsugok formation, Jaesan formation and Mesozoic Dongwhachi formation and Chungyang granite. This manganese carbonate orebody is hydrothermal replacement orebody formed by reaction of lead and zinc-bearing hydrothermal fluid and Paleozoic Janggum limestone formation. The wallrock alteration that is remarkably recognized with Pb-Zn mineralization at this hydrothermal replacement orebody consists of mainly rhodochrositization with minor of dolomitization, pyritization, sericitization and chloritization. Carbonates formed during wallrock alteration on the basis of paragenetic sequence are as followed : Ca-dolomite (Co type, wallrock) → ankerite and Ferroan ankerite (C1 type, early stage) → ankerite (C2 type) → sideroplesite (C3 type) → sideroplesite and pistomesite (C4 type, late stage). This means that Fe and Mn elements were enriched during evolution of hydrothermal fluid. Therefore, The substitution of elements during wallrock alteration beween dolomitic marble (Mg, Ca) and lead and zinc-bearing hydrothermal fluid (Fe, Mn) with paragenetic sequence is as followed : 1)Fe ↔ Mn and Mn ↔ Mg, Ca, Fe elements substitution (ankerite and Ferroan ankerite, C1 type, early stage), 2)Fe ↔ Mn, Mn ↔ Mg, Ca and Mg ↔ Ca elements substitution (ankerite, C2 type), 3)Fe ↔ Mn, Fe ↔ Ca and Mn ↔ Mg, Ca elements substitution (sideroplesite, C3 type), and 4)Fe ↔ Mg, Fe ↔ Mn and Mn ↔ Mg, Ca elements substitution (sideroplesite and pistomesite, C4 type, late stage)

Improvement of Structure and Electrochemical Properties of LiNi0.5Mn1.5O4 for High Voltage Class Cathode Material by Cr Substitution (Cr 치환을 이용한 고전압용 양극 활물질 LiNi0.5Mn1.5O4의 구조와 전기화학적 성능의 개선)

  • Eom, Won-Sob;Kim, Yool-Koo;Cho, Won-Il;Jang, Ho
    • Journal of the Korean Electrochemical Society
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    • v.8 no.2
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    • pp.82-87
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    • 2005
  • The cathode material, $LiNi_{0.5}Mn_{1.5}O_4$, for high voltage applications of Li-ion batteries exhibits impurity phases due to oxygen deficiency during the high temperature heat treatment. The impurity phase reduces the electrochemical properties of the electrode since the deficiency spinel structure disturbs the lithium ion intercalation and deintercalation. In this study, Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4(0{\leq}x{\leq}0.05)$ powders are synthesized by a sol-gel method in order to reduce the amount of the impurity phases in the $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4$. Thermal analysis of the cathode material shows that the $LiNi_{0.5}Mn_{1.5}O_4$ without Cr substitution looses $2\%$ of its weight due to oxygen deficiency but the amount of weight loss is diminished when Cr is substituted. XRD analysis also supports the reduction of the impurity phases in the cathode after chromium substitution, suggesting that the improvement of the electrochemical properties such as the capacity retention and electrochemical stability are attributed to the low content of impurity phases in the Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4.$

A Study on the Capacity Fading and the Replacement of Surface Film at the Surface of $LiMn_2O_4$ Thin Film Electrode

  • Chung Kyung Yoon;Shu Dong;Kim Kwang-Bum
    • 한국전기화학회:학술대회논문집
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    • 2002.11a
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    • pp.57-65
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    • 2002
  • The presence of tetragonal phase at the surface of $LiMn_2O_4$ pinicle due to a Jahn-Teller offset was previously reported to be one of the causes for capacity fading observed during cycling of $Li//Li_xMn_2O_4$ in 4V range. Further, it is reported that a Jahn-Teller effect in 4V range may be suppressed by substitution of Mn ions with Li ions or other transition metal ions. However, the direct evidence of the suppression of a Jahn-Teller effect in 4V range by substitution of Mn ions with other metal ions has not been reported. The dissolution and formation of surface film at the surface of $LiMn_2O_4$ electrodes also reportedly affect the capacity fading or rate capability. This study reports on the evidence of the onset and suppression of a Jahn-Teller effect in 4V range and the dissolution and formation of surface film at the surface of $LiMn_2O_4$ thin film electrodes using in situ bending beam method (BBM) in situ electrochemical quartz crystal microbalance (EQCM).

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Magnetic Properties of Mn and La-Mn Substituted Strontium Ferrite (Mn 및 La-Mn 치환 Sr 페라이트의 자기적 특성 변화)

  • 장세동;김종오;김종희
    • Journal of the Korean Magnetics Society
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    • v.11 no.6
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    • pp.267-271
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    • 2001
  • These experiments were carried out to examine the effects of elemental substitution of Mn and La-Mn on Sr-ferrite. The calcined properties for the Mn and La-Mn substitution were examined, and the sintered magnetic properties were compared with the stoichiometric condition. The magnetic properties of calcined SrM and (La-Mn)$_{0.3}$-SrM composition were as follows, respectively; M$_{s}$ : 61.06 emu/g, $_{i}$H$_{c}$ : 4.45 kOe and M$_{s}$ : 61.06 emu/g, $_{i}$H$_{c}$ : 4.46 kOe. Also, the sintered ferrite magnets of Mn$_{0.3}$-SrM and [(La-Mn)$_{0.3}$-SrM exhibited a similar properties to the stoichiometric composition but the coercivity of (La-Mn)$_{x}$-SrM was decreased rapidly with x=0.5.

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Soluble Single-Molecule Magnet: Mn12-stearate.

  • Park, Chi Dong;Jeong, Duk Yeong
    • Bulletin of the Korean Chemical Society
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    • v.22 no.6
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    • pp.611-615
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    • 2001
  • A new polynuclear complex of manganese stearate has been prepared by substitution of acetate with stearic acid. The stearate ion with long alkyl chain was used to isolate molecular $Mn_{12}$ cluster from each other. The $Mn_{12}$-stearate compound prepared is soluble in most organic solvents and resistant against water catalyzed reduction. The $Mn_{12}$-stearate compound shows similar electrochemical, magnetic properties to the pristine $Mn_{12}$-acetate.